Orange dye and process of making same.



NITE STATES PATENT rrioiz.

KARL JEDLICKA, OF BASLE, SWITZERLAND, ASSIGNOR TO THE SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF SAME PLACE.

ORANGE DYE AND PROCESS OF MAKING SAME.

SPECIFICATION formingpart of Letters Patent No. 666,095, dated January 1901- Application filed September 4, 1900. Serial No. 28,975. (SpecimengJ To aZZ whom it may concern:

Be it known that I, KARL JEDLICKA, chemist and doctor of philosophy, a citizen of the Swiss Republic, and a resident of Basie, Switzerland, have invented a new Orange Dyestuif and the Process for its Manufacture, of which the following is a clear and complete specification.

In Letters Patent No. 537,723 there has been shown that the dyestuffs of the acridin series, called acridin-yellow and benzoflavine, can be converted into alkylated dyestuffs by their treatment with alkylating agents. According to the working method and the nature of the employed alkylating agents the alkylation occurs in the amido group under formation of alkylamidoacridins of the general formula Alk 1 o,H,.oH,.N y

( N\ 0.11 X o,H,.oH,.N

(in which R stands for hydrogen or phenyl and X and Y indicate hydrogen or an alkyl radical,) or in the acridin nitrogen under formation of so-called amidoacridinium derivatives of the formula c,H,.on,.NH,

Alk 1 (in which S stands for the radical of an acid,

as Cl, SO &c., and R for hyrogen or The present invention is now based on the observation that the dyestuffs of the formulae (a) and (b) can be further alkylated. I have found that by treating the dyestuifs of the type (a) with alkylating agents in a neutral or weakly alkaline medium in absence of mineral acids a further alkyl group can be introduced in the acridin nitrogen of the dyestu fis,which are thus converted into a1 kylamidoacridiuiuin derivatives. On the other hand, the amidoacridinium derivatives of the type (b) may also be converted into alkylamidoacridinium derivatives by their alkylation in presence of acids, the alkylation occurring in this casein the amido groups. By taking the formulae (a) and (b) in consideration it will be evident that in both cases the resulting final products are identical or very analogous. In fact, the dyestufis obtained according to both ways cannot be distinguished in their chemical properties. Their constitution seems to correspond to the general formula and Y hydrogen or an alkyl group, and S a radical of an acid.)

The conversion of the alkylamidoacridinium derivatives of the formula (a) into combinations of the formula (1)) occurs in .the best manner by treating the corresponding color bases with alkyl halides, ethereal salts of alphylsulfonic acids, or dimethylsulfate in presence of suitable indifferent solvents. By working with alkyl halides ethyl alcohol is preferably employed as solvent. If ethereal salts of alphylsulfonic acids or dimethylsulfate be employed, it is useful to employ a medium free of water-as, for example, nitrobenzene. The further alkylation of the amidoacridinium compounds of the formula (I?) is preferably executed with alkylsulfates or a mixture of alcoholand concentrated sulfuric acid. The resulting dyestufis are generally orange yellow to orange red and easily soluble in water. Their solutions are not ISO tile-red crystalline mass.

.or ammonia.

(a) Conversion of the dyestuyjs of the type (a) into dyestufi s 0f thetype (0.)

I. Twenty parts patentphosphin G as base prepared, according to Example II of Letters Patent No. 537,723, from acridin-yellow and methyl sulfate, are heated with eighty parts ethyl alcohol and ten parts methyl ch1o'- rid in an autoclave for about twelve hours After the mass has cooled it is mixed with water, the alcohol at to centigrade.

distilled off, and from the filtered intensely orange-red solution the dyestuff is precipitated by an addition of sodium nitrate as a dyestuif is an orange-red powder, which dissolves easily in water to an orange yellow solution. Its aqueous solution is, contrary'to the aqueous solution of the parent material,

not changed by addition of sodium carbonate! Caustic soda precipitates the; It dyes; tannin mordanted cotton and leather fiery; 'orange-yellowto orange-red tints of great color base as orange-yellow flocks.

purity. These tints are more reddish and clearer than the tints obtained with the parent material.

By tipping the said tints obtained with the new dyestuff with ammonia or a solution of sodium carbonate they-are not changed,wh ilethe tints obtained with patentphosphin G are changed by alkalies.

II. Twenty parts -patentphosphin R .;as base prepared, according to Example II of Letters Patent No. 537,723, by energetical "alkylation of acridin yellow, are dissolved with aid of heat in fifty parts nitrobenzen'e.

about fifteen ,minutes at to centi g'rade, After the nitrobenzene has'been expelled by steam the resinous residue, which 'Nineteen parts of methyl paratoluenesulfonate are added and the mixture is heated for is pretty difficultly soluble in water and'reprecaustic soda.

*sents the paratoluenesulfonate of the formed acridinium compound,is digested with diluted The color base which is thus separated out is then dissolved in diluted hydrochloric acid and the solution obtained is heated and made weakly alkaline with ammonia in order to precipitate a small quantity of unattached parent material and filtered. From the filtrate the dyestufi is pre cipitated by addition of sodium nitrate and When dried, it is a cinnabarred powder easily soluble in. water to ancommon salt.

orange-red solution, which is not changed by sodium carbonate or ammonia. Caustic soda In dry state the alkyl halide, as'inethyl bromid, ethyl chloridv &c., and instead ofmethylparatoluenesul- 'fonate another ethereal salt of alphylsulfonic acids may be employed. The alkylation may also be prod need by dimethylsulfate,the work ing' remaining the same-as in Example II.

(6) Conversion of the dyestufls of the type (b) ,mto dyestuffs of the type (0.)

Examplez' Twenty parts of diamidoditolylmethyl-acridinium prepared by alkylating acridine-yellow with methyl chlorid or methyl paratoluenesulfonate are introduced in a cold mixture of twenty parts methyl alcohol and sixty parts concentrated sulfuric acid of 66 Baum and the whole is heated on an oilbath' for about four hours at to centigrade, being stirred the while. After the mass has cooled it is mixed with six hundred parts Water andseparated by filtration from a small quantity of an insoluble secondary product. "From-the filtered deepred solution the dyestuft is precipitated by common salt and zinc chlorid. In drystate the dyestuff is abrown-red to tile-red powder, which easily dissolves in water with an orange-yellow coloration. Toward alkalies its aqueoussolution acts in the same Way as the aqueous solution of the dyestuff prepared according toExampleI. It dyes tannin-mordanted cotton and leather orange-yellow to orange-red tints, which'fcan hardly be distinguished from the tints furnished by the dyestuif of ExampleI and possesses the same fastness to alkalies as these latter ones. If in this example the heating is effected at to centigrade,there isobtained a dyestufi of the same properties, but which furnishes more reddish tints and on this point approaches the product derived from'patentphosphin R, according to Example II.

If the diamidoditolyl methyl acridinium specified in Example III be replaced by the corresponding diamidoditolylphenyl-methylacridinium derived from benzo-flavineor the corresponding ethyl derivatives, dyestuffs of analogous properties are obtained.

The newdyestuffs are difficultly soluble in cold alcohol, more easily soluble in hot alcohol with orange coloration, insoluble in ether and benzene, and soluble in concentrated sulfuric acid of 66 Baum with a yellow coloration and a greenish-yellow fluorescence.

What I claim is- 1. The process for the manufacture of derivatives of the acridinium series, corresponding probably to the general formula (R signifying hydrogen or phenyl, X and Y standing for hydrogen or alkyl and S for a OH radical of an acid as Cl, Br, SO &c.,)

which process consists in treating alkylamidoaoridin dyestuffs with alkylating agents, substantially as described.

2. As new products, the new orange-yellow to orange-red dyestuffs, belonging to the alkylamidoacridinium series, which are ob tained by alkylating alkylamidoacridin dyestuffs and which are not precipitated from their aqueous solutions by the addition of sodium carbonate or ammonia, substantially as described.

3. As a new article of manufacture the orange dyestuff, which can be obtained by methylating alkylamidoacridin dyestuffs known in common by the name patentphosphin, and which appears, in dry state, as a brownish-red to tile-red powder, easily soluble in Water, producing an orange-yellow to orange-red solution, which is not changed by the addition of sodium carbonate or ammonia, which is soluble with difficulty in cold alcohol, but more easily soluble in hot alcohol with an orange coloration, which is insoluble in ether and benzene and soluble in concentrated sulfuric acid of 66 Baum with a yellow coloration and a greenish-yellow fluorescence, and dyes tannin-inordanted cotton in clear orange-yellow to orange-red shades, fast to the action of alkali, substantially as described.

In witness whereof I have hereunto signed my name, this 17th day of August, 1900, in the presence of the subscribing witnesses.

KARL JEDLIOKA.

Witnesses:

CLARENCE GIEEOED, GEO. GIFFORD, T. PLATNER, AMAND BITTER. 

